Active energy ray-curable urethane (meth)acrylate and active energy ray-curable composition, and uses thereof

ABSTRACT

Provided are an active energy ray-curable urethane (meth)acrylate and an active energy ray-curable composition for paints and coating agents having abrasion resistance and lubricity, and uses thereof. The curable urethane (meth)acrylate has a long chain alkyl group having 13 to 25 carbon atoms and an active energy ray-curable functional group and is modified with polycaprolactone. The urethane (meth)acrylate is obtainable by reacting an organic isocyanate having three or more isocyanate groups in one molecule, a long chain alkyl alcohol, and a polycaprolactone-modified hydroxyethyl (meth)acrylate. On the other hand, the active energy ray-curable composition contains the urethane (meth)acrylate.

BACKGROUND OF THE INVENTION

The present invention relates to an active energy ray-curable urethane(meth)acrylate and an active energy ray-curable composition.

As conventional coating agents and paints having abrasion resistance,ultraviolet curable hard coating agents, electron beam-curable hardcoating agents, silica-type hard coating agents, and two-pack typeacrylurethane soft paints are known. As conventional paints and coatingagents having lubricity, those obtainable by crosslinkingpolydimethylsiloxane graft compounds or block copolymers with anisocyanate or melamine are known.

However, in the conventional hard coating agents, crosslinking densityof the hard coating agents is increased by employing a rigid monomer.The hard coating agents form coated films through curing but the coatedfilms shrink during their curing to cause a relatively large strain.Therefore, the coated films derived from the conventional hard coatingagents exhibit a low adhesiveness to a substrate and also chipping andcracks tend to occur in the coated films.

The conventional hard coating agents form hard and brittle coated films.Therefore, in light-diffusive sheets produced by applying the hardcoating agents onto a substrate sheet made of a plastic, it becomesdifficult to subject the light-diffusive sheets to secondary processing.Moreover, at the time when the conventional hard coating agents areapplied onto a substrate sheet, the substrate sheets curl and hencecracks tend to occur at the resulting coated films.

On the other hand, in a conventional two-pack type acrylurethane softpaint, there occurs no problem such as chipping and cracks. However, thetwo-pack type acrylurethane soft paint exhibits poor workability becausethe period of time capable of applying the paint is limited and it takesa long time to cure it by drying. Furthermore, the coated film formedfrom the two-pack type acrylurethane soft paint is poor in solventresistance and blocking resistance. When polydimethylsiloxane oil isadded in order to improve blocking resistance, transparency of thecoated film, adhesiveness to a substrate, and re-coating propertiesdecrease.

In addition, the conventional paints and coating agents are veryexcellent in lubricity but it is impossible to re-coat a silk printingon coated films thereof.

BRIEF SUMMARY OF THE INVENTION

An object of the present invention is to provide an active energyray-curable urethane (meth)acrylate and active energy ray-curablecomposition which have an enhanced abrasion resistance and lubricity andare suitably usable as a paint or coating agent. Another object of thepresent invention is to provide uses of the urethane(meth)acrylate andthe composition.

For achieving the above objects, in one embodiment of the presentinvention, provided is an active energy ray-curable urethane(meth)acrylate which has an alkyl group having 13 to 25 carbon atoms andan active energy ray-curable functional group and is modified withpolycaprolactone.

The active energy ray-curable urethane (meth)acrylate is obtainable byreacting an organic isocyanate having three or more isocyanate groups inone molecule, an alkyl alcohol having 13 to 25 carbon atoms, and apolycaprolactone-modified hydroxyethyl (meth)acrylate.

It is preferred that the molar ratio of the isocyanate group of theorganic isocyanate, the hydroxyl group of the polycaprolactone-modifiedhydroxyethyl (meth)acrylate, and the hydroxyl group of the alkyl alcoholis 1:0.8 to 1.20:0.02 to 0.33.

In another embodiment of the present invention, an active energy-raycurable composition is provided. The composition comprises an activeenergy ray-curable urethane (meth)acrylate with an alkyl group having 13to 25 carbon atoms and an active energy ray-curable functional group andis modified with polycaprolactone, and at least one selected from acompound having an active energy ray-curable functional groupcopolymerizable with the urethane (meth)acrylate, organic beads,inorganic beads, and an antistatic agent.

The other embodiments and advantages of the present invention may becomeapparent from the following description along with the drawingsillustrating the examples of principle of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of a back light unit for liquid crystaldisplay using a light-diffusive sheet according to one embodiment of thepresent invention.

FIG. 2 is a cross-sectional view of an antireflection film according toone embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The following will explain one embodiment of the active energyray-curable urethane (meth)acrylate (hereinafter, referred to as curableurethane (meth)acrylate) of the present invention.

The curable urethane (meth)acrylate (A) has a long chain alkyl grouphaving 13 to 25 carbon atoms and an active energy ray-curable functionalgroup such as terminal methylene group (CH₂═) and is modified withpolycaprolactone. The curable urethane (meth)acrylate is cured by theirradiation with an active energy ray. The curable urethane(meth)acrylate is prepared by reacting an organic isocyanate (B) havingthree or more isocyanate groups in one molecule, a long-chain alkylalcohol (C) having 13 to 25 carbon atoms, and apolycaprolactone-modified hydroxyethyl (meth)acrylate (D).

The organic isocyanate (isocyanate prepolymer compound) (B) is obtainedby modifying a diisocyanate monomer (b) having two isocyanate groups.The diisocyanate monomer (b) is modified according to a modificationmethod such as isocyanurate modification, adduct modification, or biuretmodification.

Examples of the diisocyanate monomer (b) include tolylene diisocyanate(TDI) represented by the following formula (1):

naphthalene diisocyanate (NDI) represented by the following formula (2):

diphenylmethane diisocyanate (MDI) represented by the following formula(3):

isophorone diisocyanate (IPDI) represented by the following formula (4):

xylylene diisocyanate (XDI) represented by the following formula (5):

hexamethylene diisocyanate (HDI) represented by the following formula(6):

NCO—(CH₂)₆—NCO  (6)

dicyclohexylmethane diisocyanate (H-MDI) represented by the followingformula (7):

2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, andnorbornane diisocyanate methyl.

Examples of the organic isocyanate (B) subjected to isocyanuratemodification include the compounds represented by the following generalformula (8):

Examples of the organic isocyanate (B) subjected to adduct modificationinclude the compounds represented by the following general formula (9).

R has the same meaning as defined in the general formula (8).

Examples of the organic isocyanate (B) subjected to biuret modificationinclude the compounds represented by the following general formula (10):

Examples of the long-chain alkyl alcohol (C) include alcohols having along-chain alkyl group of 13 to 25 carbon atoms such as tridecanol,myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol,polyoxyethylene monostearate, polyoxyethylene cetyl ether,polyoxyethylene stearyl ether, and glycerol monostearate.

The polycaprolactone-modified hydroxyethyl (meth)acrylate (D) has anactive energy ray-curable functional group such as terminal methylenegroup (CH₂═) as shown in the following general formula (11) and isreactive with an isocyanate group.

R represents H or CH₃, and n is an integer of 1 to 25

In the general formula (11), n is an integer of 1 to 25, preferably aninteger of 2 to 5. When n is an integer of 2 to 5, the curable urethane(meth)acrylate and the composition having the curable urethane(meth)acrylate are crosslinked with a relatively low molecular weightcomponent, so that insufficient curing is suppressed and alsosatisfactory abrasion resistance and self-repairing function areexhibited.

The following will explain the synthesis method of the curable urethane(meth)acrylate.

First, an organic isocyanate (B) having three or more isocyanate groupsin one molecule is mixed and reacted with a long-chain alkyl alcohol (C)(a first step). To the reaction product is added apolycaprolactone-modified hydroxyethyl (meth)acrylate (D) and themixture is reacted (a second step). Thus, the curable urethane(meth)acrylate is obtained.

Each reaction of the first step and the second step can be carried outin a solution, and an aromatic hydrocarbon solvent such as toluene orxylene, a ketone solvent such as acetone, methyl ethyl ketone, methylisobutyl ketone, or cyclohexanone, an ester solvent such as ethylacetate, propyl acetate, isobutyl acetate, or butyl acetate, or the likecan be used singly or as a mixed solvent.

Each reaction of the first step and the second step may be also carriedout in a system without solvent or in a compound having an active energyray-curable functional group, such as styrene, isobornyl acrylate,acryloylmorpholine, diethylene glycol diacrylate, or triethylene glycoldiacrylate.

The reaction temperature of the first step or the second step ispreferably from room temperature to 100° C., and the reaction time ispreferably from 1 to 10 hours.

The organic isocyanate (B), the polycaprolactone-modified hydroxyethyl(meth)acrylate (D), and the long-chain alkyl alcohol (C) are preferablymixed so that the molar ratio of the isocyanate group of the organicisocyanate (B), the hydroxyl group of the polycaprolactone-modifiedhydroxyethyl (meth)acrylate (D), and the hydroxyl group of thelong-chain alkyl alcohol (C) becomes 1:0.8 to 1.20:0.02 to 0.33.

In the synthesis reaction of the urethane (meth)acrylate, a catalystsuch as dibutyltin dilaurate, dibutyltin diethylhexoate, or dibutyltinsulfite may be used. The amount of the catalyst to be added ispreferably from 0.01 to 1 part by weight, more preferably 0.1 to 0.5parts by weight relative to the total weight of other raw materials.Moreover, a polymerization inhibitor such as hydroquinone monomethylether may be used. The amount of the polymerization inhibitor to beadded is preferably from 0.01 to 1 part by weight relative to the totalweight of other raw materials.

The following will explain the active energy ray-curable composition(hereinafter referred to as curable composition). The essentialcomponent of this embodiment of the curable composition is the curableurethane (meth)acrylate. The curable composition includes a compound (E)having an active energy ray-curable functional group, beads (F), anantistatic agent (G), a photo-initiator (H), and other additives (I) asoptional components.

The compound (E) having an active energy ray-curable functional grouphas an active energy ray-curable functional group and is a compoundcopolymerizable with the curable urethane (meth)acrylate. Examplesthereof include monofunctional or polyfunctional monomers and oligomerseach having (meth)acryloyl group in the molecule. As such monomers andoligomers, commercially available compounds may be also employed.

Examples of the compound (E) include monofunctional monomers such asphthalic acid monohydroxyethyl acrylate, 2-ethylhexyl acrylate,phenoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxylethoxyethylacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,polycaprolactone-modified hydroxyethyl acrylate, dicyclopentenyloxyethylacrylate, N-vinylpyrrolidone, acryloylmorpholine, isobornyl acrylate,vinyl acetate, and styrene; difunctional monomers such as neopentylglycol diacrylate, 1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate,1,4-butanediol diacrylate, diethylene glycol diacrylate, triethyleneglycol diacrylate, propylene glycol diacrylate, and dipropylene glycoldiacrylate; polyfunctional monomers such as trimethylolpropanetriacrylate, pentaerythritol triacrylate, triacrylate of 3 mol propyleneoxide adduct of trimethylolpropane, triacrylate of 6 mol ethylene oxideadduct of trimethylolpropane, glycerolpropoxy triacrylate,dipentaerythritol hexaacrylate, and hexaacrylate of caprolactone adductof dipentaerythritol.

In addition, examples of the compound (E) include oligomers such asunsaturated polyesters, polyester acrylates, polyether acrylates, acrylacrylates, urethane acrylates, and epoxy acrylates.

As the beads (F), organic or inorganic beads may be employed. Examplesthereof include organic beads each made of a synthetic resin such aspolymethyl methacrylate (PMMA), nylon, or polyurethane or a rubber.Also, examples include inorganic beads each made of a metal such astitanium oxide, titanium dioxide, aluminum oxide, tin oxide, indiumoxide, zinc oxide, antimony oxide, tin oxide containing antimony, orindium oxide containing tin, or silicon dioxide or glass. The shape ofthe beads is preferably indefinite form or spherical form. Suitablematerial and size of the beads vary depending on the uses. For example,since beads each made of PMMA, titanium oxide, or silicon dioxidediffuse light uniformly, they can be used for the curable compositionfor the light-diffusive sheet 13 (upper surface) in FIG. 1. Of these,beads having an average particle size of 3 to 10 μm and made of PMMA arepreferred because of relatively high light transmittance. Beads made ofPMMA, nylon, polyurethane, or silicon dioxide can be employed for thecurable composition for the protective diffusive sheet 15 (lowersurface) in FIG. 1. Of these, beads having an average particle size of 3to 10 μm and made of PMMA, nylon or polyurethane are preferred becausethey effectively prevent the sticking to the adjacent prism sheet 14.Beads made of PMMA, titanium oxide, or silicon dioxide can be employedfor the curable composition for the protective diffusive sheet 15 (uppersurface). Of these, beads having an average particle size of 3 to 10 μmand made of PMMA are preferred because they change the output directionof light and improve brilliance. Moreover, beads made of tin oxide,indium oxide, antimony oxide, tin oxide containing antimony, or indiumoxide containing tin can impart an antistatic effect to the curablecomposition and cured product thereof. Preferred average particle sizeof the beads is from 20 to 60 nm.

Examples of the antistatic agent (G) include anionic antistatic agentssuch as alkyl phosphates, cationic antistatic agents such as quaternaryammonium salts, nonionic antistatic agents such as polyoxyethylene alkylethers, and antistatic agents containing salts of an alkali metal suchas lithium, sodium, or potassium. Of these, an antistatic agentcontaining a lithium salt is preferred.

Examples of the photo-initiator (H) include isopropyl benzoin ether,isobutyl benzoin ether, benzophenone, Michler's ketone, o-benzoylmethylbenzoate, acetophenone, 2,4-diethylthioxanthone, 2-chlorothioxanthone,ethylanthraquinone, isoamyl p-dimethylaminobenzoate, ethylp-dimethylaminobenzoate, 1-hydroxycyclohexyl phenyl ketone (e.g.,“IRGACURE 184”, a trade name of Ciba-Geigy Corp.),2-hydroxy-2-methyl-1-phenyl-propan-1-one (e.g., “DAROCURE 1173”, a tradename of Ciba-Geigy Corp.), 2,2-dimethoxy-1,2-diphenylethan-1-one (e.g.,“IRGACURE 651”, a trade name of Ciba-Geigy Corp.),2-benzyl-2-dimethylamino-1(4-morpholinophenyl)-butanone-1,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and methyl benzylformate.

Other additives (I) include a solvent, a leveling agent, an ultravioletabsorber, and the like. Example of the solvent include aromatichydrocarbon solvents such as toluene and xylene; alcohol solvents suchas methanol, ethanol, isopropyl alcohol, n-butanol, and isobutanol;ketone solvents such as acetone, methyl ethyl ketone, methyl isobutylketone, and cyclohexanone; ester solvents such as ethyl acetate, propylacetate, butyl acetate, and isobutyl acetate, and these solvents may beused singly or as a mixed solvent. Examples of the leveling agentinclude acrylic copolymers and silicone leveling agents and fluorineleveling agents. Examples of the ultraviolet absorber includebenzophenone-type, benzotriazole-type, oxalic anilide-type,triazine-type and hindered amine-type ultraviolet absorbers.

The curable composition is produced as follows.

The curable composition is produced by suitably mixing an essentialcomponent of the curable urethane (meth)acrylate with optionalcomponents (E), (F), (G), (H), and (I).

The compound (E) having an active energy ray-curable functional group ispreferably mixed in the ratio of the curable urethane (meth)acrylate tothe compound (E) having an active energy ray-curable functional group of30 to 90:5 to 35 as the ratio of solids (weight).

The beads (F) are preferably mixed in an amount of 0.01 to 100 parts byweight relative to 100 parts by weight of the components other than thebeads (F) in the curable composition.

The antistatic agent (G) is preferably mixed in an amount of 0.1 to 10parts by weight relative to 100 parts by weight of the components otherthan the antistatic agent (G) in the curable composition.

The photo-initiator (H) is preferably mixed so that the weight ratio ofthe curable urethane (meth)acrylate: the compound (E) having an activeenergy ray-curable functional group: the photo-initiator (H) becomes100:10 to 300:1 to 20.

The curable urethane (meth)acrylate and the curable composition can besuitably used as paints or coating agents, and more specifically, theyare applied onto the surfaces of electrical or electronic apparatus suchas cell phones, watches, compact discs, audio equipments, officeautomation equipments; electronic material parts such as touch panels,antireflection board for cathode ray tube; household electrical goodssuch as refrigerators, vacuum cleaners, and microwave ovens; interior ofautomobiles such as meter panels and dashboards; pre-coated metal steelplates; bodies, bumpers, spoilers, door knobs, handles, and head lampsof automobile, and fuel tanks of motorcycles; automobile parts such asplated, deposited, or sputtered aluminum wheels and door mirrors ofautomobiles; roofs of carports and roofs for natural lighting; moldedproducts, films, and sheets of plastics such as polyvinyl chloride,acrylic resin, polyethylene terephthalate (PET), polycarbonate, and ABSresin; wood products such as stairs, floors, tables, chairs, chests, andother furniture; sheet materials such as fabrics and paper.

The curable urethane (meth)acrylate and the curable composition areapplied (painting or coating) according to known methods, for example,air spraying, airless spraying, electrostatic coating, roll coater, flowcoater, and spin coating. It should be noted that the thickness of thecoated film is preferably from about 1 to 100 μm.

After being applied onto a substrate, the curable urethane(meth)acrylate and the curable composition are cured by irradiation withan active energy ray such as an ultraviolet light or an electron beam.The irradiation with an ultraviolet light is preferably conducted usinga UV light source such as a mercury lamp or a metal halide lamp so thatthe curing energy (integral light intensity) becomes from 100 to 1000mJ/cm². The irradiation with an electron beam is preferably conducted atan accelerating voltage of 150 to 250 keV so that the dose becomes from1 to 5 Mrad.

The following will explain a functional material. The functionalmaterial in this embodiment is a material cured by irradiating thecurable urethane (meth)acrylate or the curable composition with anactive energy ray such as an ultraviolet light or an electron beam, andhas a self-repairing function. Preferred irradiation conditions at theirradiation with an active energy ray are the same as the aforementionedirradiation conditions. The functional material, i.e., a cured curableurethane (meth)acrylate or curable composition can be employed in a widerange of uses.

A light-diffusive sheet will be explained below. The light-diffusivesheet in this embodiment is the sheet having a cured layer made of thecurable urethane (meth)acrylate or the curable composition on thesurface of a substrate sheet. The light-diffusive sheet can diffuseuniformly a light emitted from a light source, and can be used forliquid crystal displays, illuminating materials, advertising displaysand the like. It should be noted that as the substrate sheet, a sheet orfilm made of a synthetic resin or a glass plate can be employed.Preferred substrate sheet is a relatively highly transparent PET,polycarbonate or glass.

FIG. 1 illustrates a back light unit for liquid crystal display using alight-diffusive sheet. In the back light unit, a reflective sheet 11, alight-conducting plate 12, a first light-diffusive sheet 13, a prismsheet 14, and a protective diffusive sheet (a second light-diffusivesheet) 15 are laminated successively from the back surface of the backlight unit (lower part of FIG. 1). On the upper surface of the secondlight-diffusive sheet 15, a liquid crystal layer (not shown) isarranged. At the one end of the light-conducting plate 12, a lightsource (lamp) 16 is arranged. A light emitted from the lamp 16 entersthe light-conducting plate 12, is reflected by the reflective sheet 11,and exits from the surface of the light-conducting plate 12, and thelight finally reaches the liquid crystal layer (not shown) after passingthrough the first light-diffusive sheet 13, the prism sheet 14, and thesecond light-diffusive sheet 15, successively. The secondlight-diffusive sheet 15 has functions of diffusing the light,protecting the prism sheet 14, and preventing the dazzle of the prismsheet 14.

The following will explain an antireflection film. FIG. 2 illustrates anantireflection film 20 in this embodiment. The antireflection film 20contains a substrate film 21, a cured layer 22 comprising the curableurethane (meth)acrylate or the curable composition provided on thesubstrate film 21, and an antireflection layer 23 provided on the curedlayer 22.

As the substrate film 21, a film or sheet made of a synthetic resin or aglass plate can be employed. Of these, preferred is one made of PET,acrylic resin, polycarbonate or glass in view of transparency.

The curable composition for forming the cured layer 22 preferablycontains at least one selected from a compound (E) having an activeenergy ray-curable functional group, beads (F), a leveling agent, and anantifoaming agent. The compound (E) lowers the viscosity of the curablecomposition and makes the composition high-solid. Moreover, the compoundimproves the adhesiveness to the substrate film 21 and water resistanceof the layer 22. The beads (F) enhance the refractive index and therebyimprove the antireflective effect of the antireflection film 20. Thebeads made of titanium oxide, titanium dioxide, or zinc oxide can beemployed for the composition for the cured layer 22. Of these, beadshaving an average particle size of 10 to 100 nm and made of titaniumdioxide are preferred because of a relatively high antireflectiveeffect. The leveling agent improves leveling property of the curablecomposition. The antifoaming agent enhances antifoaming property of thecurable composition.

The antireflection layer 23 is formed from a material having arelatively low refractive index, such as an amorphousfluorine-containing polymer.

The curable urethane (meth)acrylate, the curable composition, thefunctional material, the light-diffusive sheet, and the antireflectionfilm of this embodiment have the following advantages.

(1) The curable urethane (meth)acrylate and the curable composition ofthis embodiment have an excellent abrasion resistance and lubricity, sothat they can be suitably used as paints or coating agents for theproducts wherein abrasion resistance and lubricity are required.

(2) The curable urethane (meth)acrylate and the curable compositionexhibit a small strain caused by shrinkage at curing as compared withthe conventional ultraviolet-curable hard coating agent, electronbeam-curable hard coating agent, and silica-type hard coating agent.Therefore, a coated film having some flexibility is formed from thecurable urethane (meth)acrylate and the curable composition which reducethe lowering of adhesiveness to a substrate and the occurrence ofchipping and cracks, so that secondary processing of the substrate canbe relatively easily carried out. Moreover, the curling of a relativelythin substrate such as a plastic sheet is inhibited.

(3) The curable urethane (meth)acrylate and the curable composition areone-pack type paints or coating agents, so that they have no limitationon usable period of time contrary to the conventional two-pack typeacrylic urethane soft paints and are cured within a relatively shortperiod. Therefore, the efficiency of applying operation is improved.

(4) The coated film obtained from the curable urethane (meth)acrylate orthe curable composition has a satisfactory transparency, solventresistance, blocking resistance, and re-coating property.

(5) The incorporation of the compound (E) having an active energyray-curable functional group lowers the viscosity of the curablecomposition and makes the composition high-solid. By using suchcomposition, a coated film having excellent adhesiveness to thesubstrate and solvent resistance is obtained.

(6) The curable composition containing the beads (F) can improve anantireflective effect of the antireflection film.

(7) By incorporating the antistatic agent (G), a curable compositionhaving an antistatic effect can be obtained.

(8) By using the curable composition of this embodiment, a functionalmaterial, photo-diffusive sheet, and antireflection film having theadvantages of the above (1) to (7) can be obtained.

It should be noted that the above embodiment of the present inventionmay be changed as follows.

A diisocyanate may be reacted with a long-chain alkyl alcohol (C) and apolycaprolactone-modified hydroxyethyl (meth)acrylate (D) to obtain acurable urethane (meth)acrylate.

A long-chain alkyl alcohol (C) subjected to polyether modification maybe employed. In this case, the antistatic effect of the curablecomposition is enhanced.

The antireflection film 20 has a single layered antireflection layer 23,but the antireflection film 20 may contain an antireflection layer 23comprising a plurality of layers having different refractive indices (afirst antireflection layer having a high refractive index and a secondantireflection layer having a low refractive index). For example, afirst antireflection layer containing titanium dioxide may be formed onthe layer 22 and a second antireflection layer comprising afluorine-containing polymer may be formed on the first antireflectionlayer. In this case, the antireflective effect of the antireflectionfilm is enhanced.

An over-coating layer may be further formed on the antireflection layer23 of the antireflection film 20. The antireflection layer 23 can beprotected by the over-coating layer to prevent the antireflection layerfrom fouling.

EXAMPLES

The following will explain the above embodiment of the present inventionby way of Examples and Comparative Examples. “Part(s)” means “part(s) byweight”.

Synthesis Example 1

Into a 500 ml volume flask equipped with a stirrer, a thermometer, and acondenser were charged 57.7 parts of toluene and 9.7 parts of stearylalcohol (“NAA-46”, a trade name of NOF Corporation, hydroxyl value:207), followed by heating of the mixture to 40° C. After theconfirmation of thorough dissolution of stearyl alcohol, 25 parts ofhexamethylene diisocyanate (manufactured by Tokyo Kasei Kogyo Co., Ltd.)were charged and the mixture was heated to 70° C. After 30 minutes ofthe reaction at 70° C., 0.02 parts of dibutyltin laurate were charged.After the mixture was maintained at the same temperature for 3 hours,100 parts of polycaprolactone-modified hydroxyethyl acrylate (“PLACCELFA2D”, a trade name of Daicel Chemical Industries, Ltd., hydroxyl value:163), 0.02 parts of dibutyltin laurate, and 0.02 parts of hydroquinonemonomethyl ether were charged and the mixture was maintained at 70° C.for 3 hours to complete the reaction. By adding 77 parts of toluene, aurethane acrylate containing 50% by weight of solid was obtained.

Synthesis Example 2

Into a flask similar to the flask in Synthesis Example 1 were charged60.8 parts of toluene and 8.4 parts of stearyl alcohol (NAA-46),followed by heating of the mixture to 40° C. After the confirmation ofthorough dissolution of stearyl alcohol, 50 parts of hexamethylenediisocyanate subjected to isocyanurate modification (“TAKENATE D-170N” atrade name of Takeda Chemical Industries, Ltd., NCO %: 20.9) werecharged and the mixture was heated to 70° C. After 30 minutes of thereaction at the same temperature, 0.02 parts of dibutyltin laurate wascharged. After the mixture was maintained at the same temperature for 3hours, 83.5 parts of polycaprolactone-modified hydroxyethyl acrylate(PLACCEL FA2D), 0.02 parts of dibutyltin laurate, and 0.02 parts ofhydroquinone monomethyl ether were charged. The mixture was maintainedat 70° C. for 3 hours to complete the reaction, and 81.1 parts oftoluene were added to obtain a urethane acrylate containing 50% byweight of solid.

Synthesis Example 3

Into a flask similar to the flask in Synthesis Example 1 were charged48.2 parts of toluene and 4.2 parts of stearyl alcohol (NAA-46),followed by heating of the mixture to 40° C. After the confirmation ofthorough dissolution of stearyl alcohol, 50 parts of hexamethylenediisocyanate subjected to isocyanurate modification (TAKENATE D-170N)were charged and the mixture was heated to 70° C. After 30 minutes ofthe reaction at the same temperature, 0.02 parts of dibutyltin lauratewere charged. After the mixture was maintained at the same temperaturefor 3 hours, 83.3 parts of polycaprolactone-modified hydroxyethylacrylate (“PLACCEL FA5”, a trade name of Daicel Chemical Industries,Ltd., hydroxyl value: 81.8), 0.02 parts of dibutyltin laurate, and 0.02parts of hydroquinone monomethyl ether were charged. The mixture wasmaintained at 70° C. for 3 hours to complete the reaction, and 64.2parts of toluene were added to obtain a urethane acrylate containing 50%by weight of solid.

Synthesis Example 4

Into a flask similar to the flask in Synthesis Example 1 were charged60.8 parts of toluene and 8.4 parts of stearyl alcohol (NAA-46),followed by heating of the mixture to 40° C. After the confirmation ofthorough dissolution of stearyl alcohol, 50 parts of hexamethylenediisocyanate subjected to isocyanurate modification (TAKENATE D-170N)were charged and the mixture was heated to 70° C. After 30 minutes ofthe reaction at the same temperature, 0.02 parts of dibutyltin lauratewere charged. After 3 hours of maintenance at the same temperature, 28parts of 2-hydroxyethyl acrylate (HEA), 0.02 parts of dibutyltinlaurate, and 0.02 parts of hydroquinone monomethyl ether were charged.The mixture was maintained at 70° C. for 3 hours to complete thereaction, and 25.6 parts of toluene were added to obtain a urethaneacrylate containing 50% by weight of solid.

Synthesis Example 5

Into a flask similar to the flask in Example 1 were charged 78.3 partsof toluene and 8.5 parts of stearyl alcohol (NAA-46), followed byheating of the mixture to 40° C. After the confirmation of thoroughdissolution of stearyl alcohol, 50 parts of hexamethylene diisocyanatesubjected to biuret modification (“DURANATE 24A-90CX” a trade name ofAsahi Kasei Corporation, N.V.: 90, NCO %: 21.2) were charged and themixture was heated to 70° C. After 30 minutes of the reaction at thesame temperature, 0.02 parts of dibutyltin laurate were charged. Afterthe mixture was maintained at the same temperature for 3 hours, 140.8parts of polycaprolactone-modified hydroxyethyl acrylate (“PLACCEL FA4”,a trade name of Daicel Chemical Industries, Ltd., hydroxyl value: 98),0.02 parts of dibutyltin laurate, and 0.02 parts of hydroquinonemonomethyl ether were charged. The mixture was maintained at 70° C. for3 hours to complete the reaction, and 111 parts of toluene were added toobtain a urethane acrylate containing 50% by weight of solid.

Synthesis Example 6

Into a flask similar to the flask in Synthesis Example 1 were charged 33parts of toluene and 4.8 parts of stearyl alcohol (NAA-46), followed byheating of the mixture to 40° C. After the confirmation of thoroughdissolution of stearyl alcohol, 50 parts of hexamethylene diisocyanatesubjected to trimethylol-propane adduct modification (“BURNOCK DN-950” atrade name of Dainippon Ink & Chemicals Incorporated, N.V.: 75, NCO %:12) were charged and the mixture was heated to 70° C. After 30 minutesof the reaction at the same temperature, 0.02 parts of dibutyltinlaurate were charged. After the mixture was maintained at the sametemperature for 3 hours, 63.9 parts of polycaprolactone-modifiedhydroxyethyl acrylate (“PLACCEL FA3”, a trade name of Daicel ChemicalIndustries, Ltd., hydroxyl value: 122), 0.02 parts of dibutyltinlaurate, and 0.02 parts of hydroquinone monomethyl ether were charged.The mixture was maintained at 70° C. for 3 hours to complete thereaction, and 60.7 parts of toluene were added to obtain a urethaneacrylate containing 50% by weight of solid.

Synthesis Example 7

Into a flask similar to the flask in Synthesis Example 1 were charged44.8 parts of toluene and 4.6 parts of stearyl alcohol (NAA-46),followed by heating of the mixture to 40° C. After the confirmation ofthorough dissolution of stearyl alcohol, 50 parts of xylylenediisocyanate subjected to trimethylol-propane adduct modification(“TAKENATE D-110N” a trade name of Takeda Chemical Industries, Ltd.,N.V.: 75, NCO %: 11.5) were charged and the mixture was heated to 70° C.After 30 minutes of the reaction at the same temperature, 0.02 parts ofdibutyltin laurate were charged. After the mixture was maintained at thesame temperature for 3 hours, 91.7 parts of polycaprolactone-modifiedhydroxyethyl acrylate (PLACCEL FA5), 0.02 parts of dibutyltin laurate,and 0.02 parts of hydroquinone monomethyl ether were charged. Themixture was maintained at 70° C. for 3 hours to complete the reaction,and 76.5 parts of toluene were added to obtain a urethane acrylatecontaining 50% by weight of solid.

Synthesis Example 8

Into a flask similar to the flask in Synthesis Example 1 were charged60.4 parts of toluene and 7.6 parts of cetyl alcohol (“NAA-44”, a tradename of NOF Corporation, hydroxyl value: 230), followed by heating ofthe mixture to 40° C. After the confirmation of thorough dissolution ofcetyl alcohol, 50 parts of hexamethylene diisocyanate subjected toisocyanurate modification (TAKENATE D-170N) were charged and the mixturewas heated to 70° C. After 30 minutes of the reaction at the sametemperature, 0.02 parts of dibutyltin laurate were charged. After themixture was maintained at the same temperature for 3 hours, 83.4 partsof polycaprolactone-modified hydroxyethyl acrylate (PLACCEL FA2D), 0.02parts of dibutyltin laurate, and 0.02 parts of hydroquinone monomethylether were charged. The mixture was maintained at 70° C. for 3 hours tocomplete the reaction, and 80.6 parts of toluene were added to obtain aurethane acrylate containing 50% by weight of solid.

Synthesis Example 9

Into a flask similar to the flask in Synthesis Example 1 were charged29.8 parts of toluene and 4.1 parts of cetyl alcohol (NAA-44), followedby heating of the mixture to 40° C. After the confirmation of thoroughdissolution of cetyl alcohol, 50 parts of isophorone diisocyanatesubjected to trimethylol-propane adduct modification (“TAKENATE D-140N”a trade name of Takeda Chemical Industries, Ltd., N.V.: 75, NCO %: 10.8)were charged and the mixture was heated to 70° C. After 30 minutes ofthe reaction at the same temperature, 0.02 parts of dibutyltin lauratewere charged. After the mixture was maintained at the same temperaturefor 3 hours, 57.1 parts of polycaprolactone-modified hydroxyethylacrylate (PLACCEL FA3), 0.02 parts of dibutyltin laurate, and 0.02 partsof hydroquinone monomethyl ether were charged. The mixture wasmaintained at 70° C. for 3 hours to complete the reaction, and 56.4parts of toluene were added to obtain a urethane acrylate containing 50%by weight of solid.

Synthesis Example 10

Into a flask similar to the flask in Synthesis Example 1 were charged61.3 parts of toluene and 9.7 parts of behenyl alcohol (“NAA-422”, atrade name of NOF Corporation, hydroxyl value: 180), followed by heatingof the mixture to 40° C. After the confirmation of thorough dissolutionof behenyl alcohol, 50 parts of hexamethylene diisocyanate subjected toisocyanurate modification (TAKENATE D-170N) were charged and the mixturewas heated to 70° C. After 30 minutes of the reaction at the sametemperature, 0.02 parts of dibutyltin laurate were charged. After themixture was maintained at the same temperature for 3 hours, 83.4 partsof polycaprolactone-modified hydroxyethyl acrylate (PLACCEL FA2D), 0.02parts of dibutyltin laurate, and 0.02 parts of hydroquinone monomethylether were charged. The mixture was maintained at 70° C. for 3 hours tocomplete the reaction, and 81.8 parts of toluene were added to obtain aurethane acrylate containing 50% by weight of solid.

Synthesis Example 11

Into a flask similar to the flask in Synthesis Example 1 were charged 65parts of toluene and 18 parts of a polyether-modified cetyl alcohol(“NONION P-208”, a trade name of NOF Corporation, hydroxyl value: 95),followed by heating of the mixture to 40° C. After the confirmation ofthorough dissolution of the polyether-modified cetyl alcohol, 50 partsof hexamethylene diisocyanate subjected to isocyanurate modification(TAKENATE D-170N) were charged and the mixture was heated to 70° C.After 30 minutes of the reaction at the same temperature, 0.02 parts ofdibutyltin laurate were charged. After the mixture was maintained at thesame temperature for 3 hours, 83.7 parts of polycaprolactone-modifiedhydroxyethyl acrylate (PLACCEL FA2D), 0.02 parts of dibutyltin laurate,and 0.02 parts of hydroquinone monomethyl ether were charged. Themixture was maintained at 70° C. for 3 hours to complete the reaction,and 86.7 parts of toluene were added to obtain a urethane acrylatecontaining 50% by weight of solid.

Synthesis Example 12

Into a flask similar to the flask in Synthesis Example 1 were charged51.7 parts of toluene, 5.8 parts of lauryl alcohol (“NAA-42”, a tradename of NOF Corporation, hydroxyl value: 301), and 50 parts ofhexamethylene diisocyanate subjected to isocyanurate modification(TAKENATE D-170N), and the mixture was heated to 70° C. After 30 minutesof the reaction at the same temperature, 0.02 parts of dibutyltinlaurate were charged. After the mixture was maintained at the sametemperature for 3 hours, 83.4 parts of polycaprolactone-modifiedhydroxyethyl acrylate (PLACCEL FA2D), 0.02 parts of dibutyltin laurate,and 0.02 parts of hydroquinone monomethyl ether were charged. Themixture was maintained at 70° C. for 3 hours to complete the reaction,and 79.5 parts of toluene were added to obtain a urethane acrylatecontaining 50% by weight of solid.

Synthesis Example 13

Into a flask similar to the flask in Synthesis Example 1 were charged 50parts of toluene, 50 parts of hexamethylene diisocyanate subjected toisocyanurate modification (TAKENATE D-170N), 94 parts ofpolycaprolactone-modified hydroxyethyl acrylate (PLACCEL FA2D), 0.02parts of dibutyltin laurate, and 0.02 parts of hydroquinone monomethylether. The mixture was maintained at 70° C. for 5 hours to complete thereaction, and 94 parts of toluene were added to obtain a urethaneacrylate containing 50% by weight of solid.

Synthesis Example 14

Into a flask similar to the flask in Synthesis Example 1 were charged61.6 parts of toluene and 1.4 parts of stearyl alcohol (NAA-46),followed by heating of the mixture to 40° C. After the confirmation ofthorough dissolution of stearyl alcohol, 50 parts of hexamethylenediisocyanate subjected to isocyanurate modification (TAKENATE D-170N)were charged and the mixture was heated to 70° C. After 30 minutes ofthe reaction at the same temperature, 0.02 parts of dibutyltin lauratewere charged. After the mixture was maintained at the same temperaturefor 3 hours, 92.3 parts of polycaprolactone-modified hydroxyethylacrylate (PLACCEL FA2D), 0.02 parts of dibutyltin laurate, and 0.02parts of hydroquinone monomethyl ether were charged. The mixture wasmaintained at 70° C. for 3 hours to complete the reaction, and 82.1parts of toluene were added to obtain a urethane acrylate containing 50%by weight of solid.

Synthesis Example 15

Into a flask similar to the flask in Synthesis Example 1 were charged59.5 parts of toluene and 20 parts of stearyl alcohol (NAA-46), followedby heating of the mixture to 40° C. After the confirmation of thoroughdissolution of stearyl alcohol, 50 parts of hexamethylene diisocyanatesubjected to isocyanurate modification (TAKENATE D-170N) were chargedand the mixture was heated to 70° C. After 30 minutes of the reaction atthe same temperature, 0.02 parts of dibutyltin laurate were charged.After the mixture was maintained at the same temperature for 3 hours,68.8 parts of polycaprolactone-modified hydroxyethyl acrylate (PLACCELFA2D), 0.02 parts of dibutyltin laurate, and 0.02 parts of hydroquinonemonomethyl ether were charged. The mixture was maintained at 70° C. for3 hours to complete the reaction, and 79.3 parts of toluene were addedto obtain a urethane acrylate containing 50% by weight of solid.

Synthesis Example 16

Into a flask similar to the flask in Synthesis Example 1 were charged61.7 parts of toluene and 0.6 parts of stearyl alcohol (NAA-46),followed by heating of the mixture to 40° C. After the confirmation ofthorough dissolution of stearyl alcohol, 50 parts of hexamethylenediisocyanate subjected to isocyanurate modification (TAKENATE D-170N)were charged and the mixture was heated to 70° C. After 30 minutes ofthe reaction at the same temperature, 0.02 parts of dibutyltin lauratewere charged. After the mixture was maintained at the same temperaturefor 3 hours, 93.4 parts of polycaprolactone-modified hydroxyethylacrylate (PLACCEL FA2D), 0.02 parts of dibutyltin laurate, and 0.02parts of hydroquinone monomethyl ether were charged. The mixture wasmaintained at 70° C. for 3 hours to complete the reaction, and 82.3parts of toluene were added to obtain a urethane acrylate containing 50%by weight of solid.

Synthesis Example 17

Into a flask similar to the flask in Synthesis Example 1 were charged 59parts of toluene and 24 parts of stearyl alcohol (NAA-46), followed byheating of the mixture to 40° C. After the confirmation of thoroughdissolution of stearyl alcohol, 50 parts of hexamethylene diisocyanatesubjected to isocyanurate modification (TAKENATE D-170N) were chargedand the mixture was heated to 70° C. After 30 minutes of the reaction atthe same temperature, 0.02 parts of dibutyltin laurate were charged.After the mixture was maintained at the same temperature for 3 hours,63.7 parts of polycaprolactone-modified hydroxyethyl acrylate (PLACCELFA2D), 0.02 parts of dibutyltin laurate, and 0.02 parts of hydroquinonemonomethyl ether were charged. The mixture was maintained at 70° C. for3 hours to complete the reaction, and 78.7 parts of toluene were addedto obtain a urethane acrylate containing 50% by weight of solid.

Synthesis Example 18

Into a flask similar to the flask in Synthesis Example 1 were charged62.3 parts of toluene and 8.4 parts of stearyl alcohol (NAA-46),followed by heating of the mixture to 40 C. After the confirmation ofthorough dissolution of stearyl alcohol, 50 parts of hexamethylenediisocyanate subjected to isocyanurate modification (TAKENATE D-170N)were charged and the mixture was heated to 70 C. After 30 minutes of thereaction at the same temperature, 0.02 parts of dibutyltin laurate werecharged. After the mixture was maintained at the same temperature for 3hours, 86.9 parts of polycaprolactone-modified hydroxyethyl(meth)acrylate (“PLACCEL FM2D”, a trade name of Daicel ChemicalIndustries, Ltd., hydroxyl value: 157), 0.02 parts of dibutyltinlaurate, and 0.02 parts of hydroquinone monomethyl ether were charged.The mixture was maintained at 70 C. for 3 hours to complete thereaction, and 83 parts of toluene were added to obtain a urethanemethacrylate containing 50% by weight of solid.

Synthesis Example 19

Into a flask similar to the flask in Synthesis Example 1 were charged60.7 parts of toluene and 4.2 parts of myristyl alcohol (manufactured byTokyo Kasei Kogyo Co., Ltd., super-high grade reagent, melting point 40°C.), followed by heating of the mixture to 40° C. After the confirmationof thorough dissolution of myristyl alcohol, 50 parts of hexamethylenediisocyanate subjected to isocyanurate modification (TAKENATE D-170N)were charged and the mixture was heated to 70° C. After 30 minutes ofthe reaction at the same temperature, 0.02 parts of dibutyltin lauratewere charged. After the mixture was maintained at the same temperaturefor 3 hours, 87.4 parts of polycaprolactone-modified hydroxyethylacrylate (PLACCEL FA2D), 0.02 parts of dibutyltin laurate, and 0.02parts of hydroquinone monomethyl ether were charged. The mixture wasmaintained at 70° C. for 3 hours to complete the reaction, and 80.9parts of toluene were added to obtain a urethane acrylate containing 50%by weight of solid.

Synthesis Example 20

Into a flask similar to the flask in Synthesis Example 1 were charged59.6 parts of toluene and 4.2 parts of tridecanol (manufactured by TokyoKasei Kogyo Co., Ltd., super-high grade reagent), followed by heating ofthe mixture to 40° C. After the confirmation of thorough dissolution oftridecanol, 50 parts of hexamethylene diisocyanate subjected toisocyanurate modification (TAKENATE D-170N) were charged and the mixturewas heated to 70° C. After 30 minutes of the reaction at the sametemperature, 0.02 parts of dibutyltin laurate were charged. After themixture was maintained at the same temperature for 3 hours, 87.4 partsof polycaprolactone-modified hydroxyethyl acrylate (PLACCEL FA2D), 0.02parts of dibutyltin laurate, and 0.02 parts of hydroquinone monomethylether were charged. The mixture was maintained at 70° C. for 3 hours tocomplete the reaction, and 80.9 parts of toluene were added to obtain aurethane acrylate containing 50% by weight of solid.

Synthesis Example 21

Into a flask similar to the flask in Synthesis Example 1 were charged62.0 parts of toluene and 6.0 parts of a polyoxyethylene monostearate(“NONION S-2”, a trade name of NOF Corporation), followed by stirring ofthe mixture. After the confirmation of thorough dissolution of thepolyoxyethylene monostearate, 50 parts of hexamethylene diisocyanatesubjected to isocyanurate modification (TAKENATE D-170N) were chargedand the mixture was heated to 70° C. After 30 minutes of the reaction atthe same temperature, 0.02 parts of dibutyltin laurate were charged.After the mixture was maintained at the same temperature for 3 hours,88.6 parts of polycaprolactone-modified hydroxyethyl acrylate (PLACCELFA2D), 0.02 parts of dibutyltin laurate, and 0.02 parts of hydroquinonemonomethyl ether were charged. The mixture was maintained at 70° C. for3 hours to complete the reaction, and 82.6 parts of toluene were addedto obtain a urethane acrylate containing 50% by weight of solid.

Synthesis Example 22

Into a flask similar to the flask in Synthesis Example 1 were charged62.6 parts of toluene and 7.3 parts of a polyoxyethylene cetyl ether(“NONION P-205”, a trade name of NOF Corporation), followed by heatingof the mixture to 40° C. After the confirmation of thorough dissolutionof the polyoxyethylene cetyl ether, 50 parts of hexamethylenediisocyanate subjected to isocyanurate modification (TAKENATE D-170N)were charged and the mixture was heated to 70° C. After 30 minutes ofthe reaction at the same temperature, 0.02 parts of dibutyltin lauratewere charged. After the mixture was maintained at the same temperaturefor 3 hours, 88.8 parts of polycaprolactone-modified hydroxyethylacrylate (PLACCEL FA2D), 0.02 parts of dibutyltin laurate, and 0.02parts of hydroquinone monomethyl ether were charged. The mixture wasmaintained at 70° C. for 3 hours to complete the reaction, and 83.5parts of toluene were added to obtain a urethane acrylate containing 50%by weight of solid.

Table 1 shows part of the synthesis conditions in Synthesis Examples 1to 22.

TABLE 1 (D) (B) Polycaprolactone- Organic modified (C) Synthesisisocyanate hydroxyethyl Long-chain alkyl Example (modified type)(meth)acrylate alcohol (B):(D):(C)* 1 HDI FA2D Stearyl alcohol1:0.98:0.12 (—) 2 HDI FA2D Stearyl alcohol 1:0.98:0.12 (Isocyanurate) 3HDI FA5 Stearyl alcohol 1:0.97:0.12 (Isocyanurate) 4 HDI HEA Stearylalcohol 1:0.98:0.12 (Isocyanurate) 5 HDI FA4 Stearyl alcohol 1:0.98:0.12(Biuret) 6 HDI FA3 Stearyl alcohol 1:0.98:0.12 (TMP adduct) 7 XDI FA5Stearyl alcohol 1:0.98:0.12 (TMP adduct) 8 HDI FA2D Cetyl alcohol1:0.97:0.13 (Isocyanurate) 9 IPDI FA3 Cetyl alcohol 1:0.97:0.13 (TMPadduct) 10 HDI FA2D Behenyl alcohol 1:0.97:0.13 (Isocyanurate) 11 HDIFA2D Polyether-modified 1:0.98:0.12 (Isocyanurate) cetyl alcohol 12 HDIFA2D Lauryl alcohol 1:0.97:0.13 (Isocyanurate) 13 HDI FA2D None 1:1.1:0(Isocyanurate) 14 HDI FA2D Stearyl alcohol 1:1.08:0.02 (Isocyanurate) 15HDI FA2D Stearyl alcohol 1:0.8:0.3 (Isocyanurate) 16 HDI FA2D Stearylalcohol 1:1.09:0.01 (isocyanurate) 17 HDI FA2D Stearyl alcohol1:0.74:0.36 (Isocyanurate) 18 HDI FM2D Stearyl alcohol 1:0.98:0.12(Isocyanurate) 19 HDI FA2D Myristyl alcohol 1:1.02:0.08 (Isocyanurate)20 HDI FA2D Tridecanol 1:1.02:0.08 (Isocyanurate) 21 HDI FA2DPolyoxyethylene 1:1.04:0.06 (Isocyanurate) monostearate 22 HDI FA2DPolyoxyethylene 1:1.04:0.06 (Isocyanurate) cetyl ether *isocyanate groupof (B):hydroxyl group of (D):hydroxyl group of (C) [molar ratio]

Example 1

By blending 20 parts of phthalic acid monohydroxyethyl acrylate(“M-5400”, a trade name of Toagosei Co., Ltd.), 20 parts of toluene, and3 parts of a photo-initiator (“IRGACURE 184”, a trade name of Ciba-GeigyCorp.) in 100 parts of the urethane acrylate obtained in SynthesisExample 1, a curable composition having 50% by weight of solid wasobtained.

Example 2

By blending 3.5 parts of an antistatic agent (“CATION B-4”, a trade nameof NOF Corporation) in 100 parts of the curable composition obtained inExample 1, a curable composition having 50% by weight of solid wasobtained.

Example 3

By blending 3 parts of a photo-initiator (IRGACURE 184) in 100 parts ofthe urethane acrylate obtained in Synthesis Example 2, a curablecomposition having 50% by weight of solid was obtained.

Example 4

By blending 4 parts of an antistatic agent (CATION B-4) and 2 parts of aphoto-initiator (IRGACURE 184) in 100 parts of the urethane acrylateobtained in Synthesis Example 2, a curable composition having 50% byweight of solid was obtained.

Example 5

20 parts of phthalic acid monohydroxyethyl acrylate (M-5400), 0.02 partsof PMMA beads (“GM-0630H”, a trade name of Ganz Chemical Co., Ltd.), 20parts of toluene, and 0.8 parts of a photo-initiator (IRGACURE 184) wereblended in 100 parts of the curable composition obtained in Example 4,and the mixture was sufficiently dispersed by means of a dispersionmixing machine, whereby a curable composition having 50% by weight ofsolid was obtained.

Example 6

35 parts of PMMA beads (GM-0630H), 35 parts of toluene, and 2 parts of aphoto-initiator (IRGACURE 184) were blended in 100 parts of the urethaneacrylate obtained in Synthesis Example 3, and the mixture wassufficiently dispersed by means of a dispersion mixing machine, wherebya curable composition having 50% by weight of solid was obtained.

Example 7

By blending 2.5 parts of an antistatic agent (CATION B-4) in 100 partsof the curable composition obtained in Example 6, a curable compositionhaving 50% by weight of solid was obtained.

Example 8

By blending 40 parts of phthalic acid monohydroxyethyl acrylate(M-5400), 6 parts of dipentaerythritol hexaacrylate (“M-400”, a tradename of Toagosei Chemical Industries, Co., Ltd.), 46 parts of toluene,and 3.8 parts of a photo-initiator (IRGACURE 184) in 100 parts of theurethane acrylate obtained in Synthesis Example 5, a curable compositionhaving 50% by weight of solid was obtained.

Example 9

35 parts of nylon beads (“SP-500”, a trade name of Toray Industries,Inc.) and 35 parts of toluene were blended in 100 parts of the curablecomposition obtained in Example 8, and the mixture was sufficientlydispersed by means of a dispersion mixing machine, whereby a curablecomposition having 50% by weight of solid was obtained.

Example 10

By blending 2.5 parts of an antistatic agent (CATION B-4) and 2 parts ofa photo-initiator (IRGACURE 184) in 100 parts of the urethane acrylateobtained in Synthesis Example 6, a curable composition having 50% byweight of solid was obtained.

Example 11

By blending 20 parts of phthalic acid monohydroxyethyl acrylate(M-5400), 20 parts of toluene, and 0.8 parts of a photo-initiator(IRGACURE 184) in 100 parts of the curable composition obtained inExample 10, a curable composition having 50% by weight of solid wasobtained.

Example 12

By blending 2 parts of a photo-initiator (IRGACURE 184) in 100 parts ofthe urethane acrylate obtained in Synthesis Example 7, a curablecomposition having 50% by weight of solid was obtained.

Example 13

By blending 20 parts of phthalic acid monohydroxyethyl acrylate(M-5400), 20 parts of toluene, and 0.8 parts of a photo-initiator(IRGACURE 184) in 100 parts of the curable composition obtained inExample 12, a curable composition having 50% by weight of solid wasobtained.

Example 14

By blending 0.02 parts of PNMA beads (GM-0630H) and 2.5 parts of anantistatic agent (CATION B-4) in 100 parts of the curable compositionobtained in Example 13, a curable composition having 50% by weight ofsolid was obtained.

Example 15

35 parts of PMMA beads (GM-0630H), 35 parts of toluene, and 2 parts of aphoto-initiator (IRGACURE 184) were blended in 100 parts of the urethaneacrylate obtained in Synthesis Example 8, and the mixture wassufficiently. dispersed by means of a dispersion mixing machine, wherebya curable composition having 50% by weight of solid was obtained.

Example 16

By blending 12 parts of phthalic acid monohydroxyethyl acrylate(M-5400), 12 parts of toluene, and 0.5 parts of a photo-initiator(IRGACURE 184) in 100 parts of the curable composition obtained inExample 15, a curable composition having 50% by weight of solid wasobtained.

Example 17

By blending 2.5 parts of an antistatic agent (CATION B-4) and 2 parts ofa photo-initiator (IRGACURE 184) in 100 parts of the urethane acrylateobtained in Synthesis Example 9, a curable composition having 50% byweight of solid was obtained.

Example 18

By blending 20 parts of phthalic acid monohydroxyethyl acrylate(M-5400), 20 parts of toluene, and 0.8 parts of a photo-initiator(IRGACURE 184) in 100 parts of the curable composition obtained inExample 17, a curable composition having 50% by weight of solid wasobtained.

Example 19

By blending 0.02 parts of PMMA beads (GM-0630H) and 2 parts of aphoto-initiator (IRGACURE 184) in 100 parts of the urethane acrylateobtained in Synthesis Example 10, a curable composition having 50% byweight of solid was obtained.

Example 20

By blending 2.5 parts of an antistatic agent (CATION B-4) in 100 partsof the curable composition obtained in Example 19, a curable compositionhaving 50% by weight of solid was obtained.

Example 21

By blending 2 parts of a photo-initiator (IRGACURE 184) in 100 parts ofthe urethane acrylate obtained in Synthesis Example 11, a curablecomposition having 50% by weight of solid was obtained.

Example 22

0.02 parts of nylon beads (SP-500) and 2 parts of a photo-initiator(IRGACURE 184) were blended in 100 parts of the urethane acrylateobtained in Synthesis Example 11, and the mixture was sufficientlydispersed by means of a dispersion mixing machine, whereby a curablecomposition having 50% by weight of solid was obtained.

Example 23

By blending 20 parts of phthalic acid monohydroxyethyl acrylate(M-5400), 3 parts of dipentaerythritol hexaacrylate (M-400), 3.7 partsof an antistatic agent (CATION B-4), 23 parts of toluene, and 0.9 partsof a photo-initiator (IRGACURE 184) in 100 parts of the curablecomposition obtained in Example 22, a curable composition having 50% byweight of solid was obtained.

Example 24

By blending 2 parts of a photo-initiator (IRGACURE 184) in 100 parts ofthe urethane acrylate obtained in Synthesis Example 14, a curablecomposition having 50% by weight of solid was obtained.

Example 25

0.02 parts of PMMA beads (GM-0630H) were blended in 100 parts of thecurable composition obtained in Example 24, and the mixture wassufficiently dispersed by means of a dispersion mixing machine, wherebya curable composition having 50% by weight of solid was obtained.

Example 26

By blending 2.5 parts of an antistatic agent (CATION B-4) in 100 partsof the curable composition obtained in Example 25, a curable compositionhaving 50% by weight of solid was obtained.

Example 27

By blending 20 parts of phthalic acid monohydroxyethyl acrylate(M-5400), 3 parts of dipentaerythritol hexaacrylate (M-400), 23 parts oftoluene, and 2.9 parts of a photo-initiator (IRGACURE 184) in 100 partsof the urethane acrylate obtained in Synthesis Example 15, a curablecomposition having 50% by weight of solid was obtained.

Example 28

0.02 parts of PMMA beads (GM-0630H) were blended in 100 parts of thecurable composition obtained in Example 27, and the mixture wassufficiently dispersed by means of a dispersion mixing machine, wherebya curable composition having 50% by weight of solid was obtained.

Example 29

The urethane acrylate obtained in Synthesis Example 18 was employed asit was, as a curable composition.

Example 30

20 parts of phthalic acid monohydroxyethyl acrylate (M-5400), 0.02 partsof PMMA beads (GM-0630H), and 3.5 parts of an antistatic agent (CATIONB-4) were blended in 100 parts of the curable composition obtained inExample 29, and the mixture was sufficiently dispersed by means of adispersion mixing machine, whereby a curable composition was obtained.

Example 31

By blending 20 parts of phthalic acid monohydroxyethyl acrylate(M-5400), 3 parts of dipentaerythritol hexaacrylate (M-400), 23 parts oftoluene, and 3 parts of a photo-initiator (IRGACURE 184) in 100 parts ofthe urethane acrylate obtained in Synthesis Example 19, a curablecomposition having 50% by weight of solid was obtained.

Example 32

By blending 20 parts of phthalic acid monohydroxyethyl acrylate(M-5400), 3 parts of dipentaerythritol hexaacrylate (M-400), 23 parts oftoluene, and 3 parts of a photo-initiator (IRGACURE 184) in 100 parts ofthe urethane acrylate obtained in Synthesis Example 20, a curablecomposition having 50% by weight of solid was obtained.

Example 33

By blending 5 parts of dipentaerythritol hexaacrylate (M-400), 8 partsof an active energy ray-reactive antistatic agent (“NK oligoU-601LPA60”, a trade name of Shin-Nakamura Chemicals Co., Ltd.), 13parts of toluene, and 2 parts of a photo-initiator (IRGACURE 184) in 100parts of the urethane acrylate obtained in Synthesis Example 21, acurable composition having 50% by weight of solid was obtained.

Example 34

By blending 5 parts of dipentaerythritol hexaacrylate (M-400), 3 partsof an antistatic agent (“SANKONOL PRO-10R”, a trade name of Sanko KagakuKogyo Co., Ltd.), 8 parts of toluene, and 2 parts of a photo-initiator(IRGACURE 184) in 100 parts of the urethane acrylate obtained inSynthesis Example 21, a curable composition having 50% by weight ofsolid was obtained.

Example 35

By blending 5 parts of dipentaerythritol hexaacrylate (M-400), 8 partsof an active energy ray-reactive antistatic agent (NK oligo U-601LPA60),13 parts of toluene, and 2 parts of a photo-initiator (IRGACURE 184) in100 parts of the urethane acrylate obtained in Synthesis Example 22, acurable composition having 50% by weight of solid was obtained.

Comparative Example 1

By blending 2 parts of a photo-initiator (IRGACURE 184) in 100 parts ofthe urethane acrylate obtained in Synthesis Example 4, a curablecomposition having 50% by weight of solid was obtained.

Comparative Example 2

20 parts of phthalic acid monohydroxyethyl acrylate (M-5400), 0.02 partsof PMMA beads (GM-0630H), 20 parts of toluene, 3.5 parts of anantistatic agent (CATION B-4), and 0.8 parts of a photo-initiator(IRGACURE 184) were blended in 100 parts of the curable compositionobtained in Comparative Example 1, and the mixture was sufficientlydispersed by means of a dispersion mixing machine, whereby a curablecomposition having 50% by weight of solid was obtained.

Comparative Example 3

By blending 20 parts of phthalic acid monohydroxyethyl acrylate(M-5400), 20 parts of toluene, and 2.8 parts of a photo-initiator(IRGACURE 184) in 100 parts of the urethane acrylate obtained inSynthesis Example 12, a curable composition having 50% by weight ofsolid was obtained.

Comparative Example 4

0.02 parts of PMMA beads (GM-0630H) and 2.5 parts of an antistatic agent(CATION B-4) were blended in 100 parts of the curable compositionobtained in Comparative Example 3, and the mixture was sufficientlydispersed by means of a dispersion mixing machine, whereby a curablecomposition having 50% by weight of solid was obtained.

Comparative Example 5

35 parts of nylon beads (SP-500), 35 parts of toluene, and 2 parts of aphoto-initiator (IRGACURE 184) were blended in 100 parts of the urethaneacrylate obtained in Synthesis Example 13, and the mixture wassufficiently dispersed by means of a dispersion mixing machine, wherebya curable composition having 50% by weight of solid was obtained.

Comparative Example 6

By blending 20 parts of phthalic acid monohydroxyethyl acrylate(M-5400), 3 parts of dipentaerythritol hexaacrylate (M-400), 3.7 partsof an antistatic agent (CATION B-4), 23 parts of toluene, and 2.9 partsof a photo-initiator (IRGACURE 184) in 100 parts of the curablecomposition obtained in Comparative Example 5, a curable compositionhaving 50% by weight of solid was obtained.

Comparative Example 7

By blending 20 parts of phthalic acid monohydroxyethyl acrylate(M-5400), 3.5 parts of an antistatic agent (CATION B-4), 20 parts oftoluene, and 2.8 parts of a photo-initiator (IRGACURE 184) in 100 partsof the urethane acrylate obtained in Synthesis Example 16, a curablecomposition having 50% by weight of solid was obtained.

Comparative Example 8

0.02 parts of PMMA beads (GM-0630H) were blended in 100 parts of thecurable composition obtained in Comparative Example 7, and the mixturewas sufficiently dispersed by means of a dispersion mixing machine,whereby a curable composition having 50% by weight of solid wasobtained.

Comparative Example 9

By blending 2.5 parts of an antistatic agent (CATION B-4) and 2 parts ofa photo-initiator (IRGACURE 184) in 100 parts of the urethane acrylateobtained in Synthesis Example 17, a curable composition having 50% byweight of solid was obtained.

Comparative Example 10

By blending 20 parts of phthalic acid monohydroxyethyl acrylate(M-5400), 0.02 parts of PMMA beads (GM-0630H), 20 parts of toluene, and0.8 parts of a photo-initiator (IRGACURE 184) in 100 parts of thecurable composition obtained in Comparative Example 9, a curablecomposition having 50% by weight of solid was obtained.

Comparative Example 11

80 parts of dipentaerythritol hexaacrylate (M-400), 20 parts oftetrahydrofurfuryl acrylate (“LIGHT-ACRYLATE THF-A”, a trade name ofKyoeisha Chemical Co., Ltd.), 100 parts of toluene, and 4 parts of aphoto-initiator (IRGACURE 184) were blended, whereby a curablecomposition (a hard-coating agent) having 50% by weight of solid wasobtained.

Comparative Example 12

100 parts of an acrylic polyol (“GAMERON 18-300”, a trade name of NatocoCo., Ltd.) and 20 parts of an isocyanate curing agent (“GAMERON curingagent 18-001”, a trade name of Natoco Co., Ltd.) were blended, whereby atwo-pack type acrylurethane soft paint was obtained.

The following Tables 2 and 3 show part of the components to be mixed inthe above Examples and Comparative Examples.

TABLE 2 (E) (A) Compound having active Active energy ray- energyray-curable (G) (H) curable urethane functional group (F) AntistaticPhoto- Example (meth)acrylate copolymerizable with (A) Beads agentinitiator 1 Synthesis Exp. 1 ∘ — — ∘ 2 Synthesis Exp. 1 ∘ — ∘ ∘ 3Synthesis Exp. 2 — — — ∘ 4 Synthesis Exp. 2 — — ∘ ∘ 5 Synthesis Exp. 2 ∘∘ ∘ ∘ 6 Synthesis Exp. 3 — ∘ — ∘ 7 Synthesis Exp. 3 — ∘ ∘ ∘ 8 SynthesisExp. 5 ∘ — — ∘ 9 Synthesis Exp. 5 ∘ ∘ — ∘ 10 Synthesis Exp. 6 — — ∘ ∘ 11Synthesis Exp. 6 ∘ — ∘ ∘ 12 Synthesis Exp. 7 — — — ∘ 13 Synthesis Exp. 7∘ — — ∘ 14 Synthesis Exp. 7 ∘ ∘ ∘ ∘ 15 Synthesis Exp. 8 — ∘ — ∘ 16Synthesis Exp. 8 ∘ ∘ — ∘ 17 Synthesis Exp. 9 — — ∘ ∘ 18 Synthesis Exp. 9∘ — ∘ ∘ 19 Synthesis Exp. 10 — ∘ — ∘ 20 Synthesis Exp. 10 — ∘ ∘ ∘ 21Synthesis Exp. 11 — — — ∘ 22 Synthesis Exp. 11 — ∘ — ∘ 23 Synthesis Exp.11 ∘ ∘ ∘ ∘ 24 Synthesis Exp. 14 — — — ∘ 25 Synthesis Exp. 14 — ∘ — ∘ 26Synthesis Exp. 14 — ∘ ∘ ∘ 27 Synthesis Exp. 15 ∘ — — ∘ 28 Synthesis Exp.15 ∘ ∘ — ∘ 29 Synthesis Exp. 18 — — — — 30 Synthesis Exp. 18 ∘ ∘ ∘ — 31Synthesis Exp. 19 ∘ — — ∘ 32 Synthesis Exp. 20 ∘ — — ∘ 33 Synthesis Exp.21 ∘ — ∘ ∘ 34 Synthesis Exp. 21 ∘ — ∘ ∘ 35 Synthesis Exp. 22 ∘ — ∘ ∘

TABLE 3 (E) (A) Compound having active Active energy ray- energyray-curable (G) (H) Comparative curable urethane functional group (F)Antistatic Photo- ExampleNo. (meth)acrylate copolymerizable with (A)Beads agent initiator 1 Synthesis Example 4 — — — ∘ 2 Synthesis Example4 ∘ ∘ ∘ ∘ 3 Synthesis Example 12 ∘ — — ∘ 4 Synthesis Example 12 ∘ ∘ ∘ ∘5 Synthesis Example 13 — ∘ — ∘ 6 Synthesis Example 13 ∘ ∘ ∘ ∘ 7Synthesis Example 16 ∘ — ∘ ∘ 8 Synthesis Example 16 ∘ ∘ ∘ ∘ 9 SynthesisExample 17 — — ∘ ∘ 10 Synthesis Example 17 ∘ ∘ ∘ ∘ 11 Common hardcoating agent 12 Common two-pack type acrylurethane soft paint

(Preparation of Test Plate)

Each of the compositions of Examples 1 to 35 and Comparative Examples 1to 12 was applied onto an easily adhering PET plate, a polycarbonateplate, and an aluminum plate, and dried, and cured to prepare a testplate. It should be noted that in the case of an easily adhering PETplate, the composition was applied by a bar coater so that the filmthickness became from 5 to 7 μm at drying. In the case of apolycarbonate or aluminum plate, the composition was applied by sprayingso that the film thickness became from 10 to 15 μm at drying. The testplates other than the plate of Comparative Example 12 were subjected todrying treatment in a drying oven of 60° C. over the period of 1 minute.The test plate of Comparative Example 12 was subjected to dryingtreatment at 120° C. over the period of 15 minutes. The compositionsother than those of Examples 29 and 30 were cured by conveying the testplates at a conveyer speed of 5 m/minute in a UV drying oven having theoutput of 80 W/cm of one light. In the case of those of Examples 29 and30, the compositions were cured by irradiating the test plates with anelectron beam at an accelerating voltage of 150 keV and an irradiationdose of 3 Mrad.

(Test Example)

Transparency of each paint, i.e., composition, transparency,adhesiveness, moisture resistance, solvent resistance, self-repairingfunction, blocking property, lubricity, flexure resistance, acidresistance, and alkali resistance of the coated film of each test plate,and damaging property to the prism sheet were evaluated at 5 ranks, andalso abrasion resistance (haze value) and surface resistance value weremeasured.

Using the test plates made of a polycarbonate plate or aluminum plate,self-repairing function and flexure resistance were evaluated. The otherevaluations and measurements were carried out using the test plates madeof an easily adhering PET plate.

The paint transparency and coated film transparency were visuallyevaluated. The adhesiveness was evaluated according to a cross-cutcellophane-tape peeling test of JIS K5400. The moisture resistance wasevaluated on the test plate after allowing it to stand at 50° C. and arelative humidity of 98% for 500 hours. The solvent resistance wasevaluated by rubbing the plate a hundred times with toluene. Theabrasion resistance was judged by the haze value (%) after 50 times ofthe rubbing with a 500 g load using #000 steel wool. The self-repairingfunction was evaluated by scratching the coated film with a nail,allowing the plate to stand at room temperature for 30 minutes, and thenthe degree of restoration of the scratch was visually evaluated. Theblocking property was evaluated on the test plate to which a load of 200g/cm² was exerted at 60° C. over the period of 24 hours using aconstant-load compressing machine. The lubricity was evaluated bytouching the plate with a finger. The flexure resistance was evaluatedby folding the test plate to 0T. The acid resistance was evaluated by a24-hour spot test using 0.1 N sulfuric acid. The alkali resistance wasevaluated by a 24-hour spot test using 0.1 N sodium hydroxide. Thedamaging property to the prism sheet was evaluated by testing the plateten times with a 200 g load using a friction-fastness testing machine.The surface resistance value was measured by means of a high resistancemeter manufactured by Advantest Corporation. The results of theseevaluations and measurements are shown in the following Tables 4 to 7.The symbols in the following tables mean as follows. ⊚: extremely good,◯: good, □: almost good, Δ: poor, X particularly poor

TABLE 4 Example 1 2 3 4 5 6 7 8 9 10 11 12 Paint transparency ∘ ∘ ∘ ∘ —— — ∘ — ∘ ∘ ∘ Coated film transparency ∘ ∘ ∘ ∘ — — — ∘ — ∘ ∘ ∘Adhesiveness ⊚ ⊚ ∘ ∘ ⊚ ∘ ∘ ⊚ ⊚ ∘ ⊚ ∘ Moisture resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘∘ ∘ ∘ ∘ Solvent resistance □ □ ∘ ∘ ∘ ∘ ∘ ⊚ ⊚ ∘ ∘ ∘ Abrasion resistance2> 2> 2> 2> 2> 2> 2> 2> 2> 2> 2> 2> Self-repairing function □ □ ∘ ∘ ∘ ∘∘ ∘ ∘ ∘ ∘ ∘ Blocking property ∘ ∘ ∘ ∘ ∘ ∘ ∘ ⊚ ⊚ ∘ ∘ ∘ Lubricity □ □ ∘ ∘∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Flexure resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Acidresistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Alkali resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘∘ ∘ Damaging property to prism ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Surfaceresistance value (Ω) 10¹⁵< 10¹¹ 10¹⁵< 10¹¹ 10¹¹ 10¹⁵< 10¹¹ 10¹⁵< 10¹⁵<10¹¹ 10¹¹ 10¹⁵<

TABLE 5 Example 13 14 15 16 17 18 19 20 21 22 23 24 Paint transparency ∘— — — ∘ ∘ — — ∘ — — ∘ Coated film transparency ∘ — — — ∘ ∘ — — ∘ — — ∘Adhesiveness ⊚ ⊚ ∘ ⊚ ∘ ⊚ ∘ ∘ ∘ ∘ ⊚ ∘ Moisture resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘∘ ∘ ∘ ∘ Solvent resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ⊚ ∘ Abrasion resistance2> 2> 2> 2> 2> 2> 2> 2> 2> 2> 2> 2> Self-repairing function ∘ ∘ ∘ ∘ ∘ ∘∘ ∘ ∘ ∘ ∘ ∘ Blocking property ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Lubricity ∘ ∘ ∘ ∘∘ ∘ ∘ ∘ ∘ ∘ ∘ □ Flexure resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Acidresistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Alkali resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘∘ ∘ Damaging property to prism ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Surfaceresistance value (Ω) 10¹⁵< 10¹¹ 10¹⁵< 10¹⁵< 10¹¹ 10¹¹ 10¹⁵< 10¹¹ 10¹³10¹³ 10⁹ 10¹⁵<

TABLE 6 Example 25 26 27 28 29 30 31 32 33 34 35 Paint transparency — —∘ — ∘ — ∘ ∘ ∘ ∘ ∘ Coated film transparency — — ∘ — ∘ — ∘ ∘ ∘ ∘ ∘Adhesiveness ∘ ∘ ⊚ ⊚ ∘ ⊚ ∘ ∘ ∘ ∘ ∘ Moisture resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘∘ ∘ Solvent resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Abrasion resistance 2> 2>2> 2> 2> 2> 2> 2> 2> 2> 2> Self-repairing function ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘Blocking property ∘ ∘ ⊚ ⊚ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Lubricity □ □ ⊚ ⊚ ∘ ∘ □ □ ∘ ∘ ∘Flexure resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Acid resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘∘ ∘ ∘ Alkali resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Damaging property to prism∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Surface resistance value (Ω) 10¹⁵< 10¹¹ 10¹⁵<10¹⁵< 10¹⁵< 10¹¹ 10¹⁵< 10¹⁵< 10¹⁰ 10⁹ 10⁹

TABLE 7 Comparative Example 1 2 3 4 5 6 7 8 9 10 11 12 Painttransparency ∘ — ∘ — — — ∘ — Δ Δ ∘ ∘ Coated film transparency ∘ — ∘ — —— ∘ — Δ Δ ∘ ∘ Adhesiveness ∘ ∘ ∘ ⊚ ∘ ⊚ ∘ ∘ ∘ ⊚ □ ∘ Moisture resistance ∘∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Solvent resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘Abrasion resistance 8> 8> 2> 2> 2> 2> 2> 2> 2> 2> 2> 8> Self-repairingfunction x x ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ x x Blocking property ∘ ∘ x x Δ Δ Δ Δ ⊚ ⊚ ∘∘ Lubricity ∘ ∘ x x Δ Δ Δ Δ ⊚ ⊚ □ □ Flexure resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘∘ x □ Acid resistance ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Alkali resistance ∘ ∘ ∘ ∘∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Damaging property to prism ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Δ □Surface resistance value (Ω) 10¹⁵< 10¹¹ 10¹⁵< 10¹¹ 10¹⁵< 10¹¹ 10¹¹ 10¹¹10¹¹ 10¹¹ 10¹⁵< 10¹⁵<

(Consideration)

With regard to the test pieces of Examples 1 to 35, abrasion resistanceand lubricity were good and other properties were also almost good.Therefore, it was shown that the compositions of Examples 1 to 35 couldbe suitably used in the fields requiring abrasion resistance andlubricity. To the contrary, with regard to the test pieces ofComparative Examples 1 to 8 and 12, either abrasion resistance orlubricity was poor. Therefore, it was shown that the compositions ofComparative Examples 1 to 8 and 12 were not suitable for the use in thefields requiring abrasion resistance and lubricity. Moreover, withregard to the test pieces of Comparative Examples 9 to 11, abrasionresistance and lubricity were evaluated to be almost good, but otherproperties were poor. Therefore, it was shown that the compositions ofComparative Examples 9 to 11 were sometimes not suitable for the use inthe fields requiring abrasion resistance and lubricity. For example, thetest piece of Comparative Example 11 is inferior in flexure resistance,so that the composition of Comparative Example 11 is not suitable forthe substrate requiring secondary processing.

In Examples 1 and 2, solvent resistance was slightly lower compared withthose in Examples 3 to 35. Accordingly, it was shown that solventresistance could be improved by changing the number of the isocyanategroups contained in the organic isocyanate (B) molecule used as areaction raw material for the curable urethane (meth)acrylate from twoto three or more.

In Comparative Examples 1 and 2 wherein a polycaprolactone-modifiedhydroxyethyl (meth)acrylate (D) was not used as a reaction raw materialfor the urethane (meth)acrylate, abrasion resistance and self-repairingfunction were extremely low. Accordingly, it was shown that abrasionresistance and self-repairing function could be improved by using thepolycaprolactone-modified hydroxyethyl (meth)acrylate (D).

In Comparative Examples 3 and 4 wherein a long-chain alkyl alcohol (C)was not used as a reaction raw material for the urethane (meth)acrylateand Comparative Examples 5 and 6 wherein the long-chain alkyl alcohol(C) had 12 or less carbon atoms, lubricity and blocking property werelow. Accordingly, it was shown that the long-chain alkyl alcohol (C)having 13 or more carbon atoms improves lubricity and blocking property.

In Comparative Examples 7 and 8 wherein a small amount of the long-chainalkyl alcohol was added, lubricity and blocking property of the curablecomposition were low and, in Comparative Examples 9 and 10 wherein alarge amount of the long-chain alkyl alcohol was added, painttransparency and coated film transparency were low.

In Examples 21 to 23 wherein a long-chain alkyl alcohol (C) subjected topolyether modification was used, surface resistance value of the coatedfilm had a tendency to decrease, and the surface resistance valuefurther decreased by using the alkyl alcohol (C) and an antistatic agentin combination.

In the cases where the curable composition contained a compound (E)having an active energy ray-curable functional group (Examples 1, 2, 5,8, 9, 11, 13, 14, 16, 18, 23, 27, 28, and 30 to 35), it was shown thatadhesiveness and solvent resistance were improved.

In the curable compositions of Examples 33 to 35 containing a curableurethane (meth)acrylate having a polyether backbone and an antistaticagent (G) containing a lithium salt, it was shown that surfaceresistance value was one or two orders smaller than the curablecompositions each containing other common antistatic agent (G) such asanionic, cationic, or nonionic one. This is because the lithium ion inthe antistatic agent (G) interacts with the polyether backbone of thecurable urethane (meth)acrylate.

In the curable compositions of Examples 33 and 35 wherein an activeenergy ray-reactive antistatic agent was used, there existed nopossibility of the depression of function caused by bleed-out, so thatthe compositions were particularly preferred.

Example 36

A curable composition having 50% by weight of solid content was preparedfrom 100 parts of the urethane acrylate obtained in Synthesis Example 2,20 parts of phthalic acid monohydroxyethyl acrylate (M-5400), 5 parts ofdipentaerythritol hexaacrylate (M-400), 25 parts of toluene, and 3 partsof a photo-initiator (IRGACURE 184). The curable composition was appliedonto a plasma-treated PET plate (a thickness of 100 μm) by spraying.After evaporation of the solvent, the PET plate was irradiated with alight of integral light intensity of 300 mJ/cm². Thereby, a layer (athickness of 100 μm) comprising a cured curable composition was formedon the PET plate. Subsequently, a coating agent (Applying liquid A)containing 100 parts of OPSTAR JM5010 (manufactured by JSR Co., Ltd.)and 0.3 parts of a photo-initiator (IRGACURE 184) was applied onto thecured layer by spin coating. The coating agent was cured by irradiationwith a light of integral light intensity of 400 mJ/cm² to form a layer(a thickness of 0.1 μm) having a low refractive index, whereby thedesired antireflection film was obtained.

Example 37

A curable composition having 50% by weight of solid content was preparedfrom 100 parts of the urethane acrylate obtained in Synthesis Example 2,20 parts of phthalic acid monohydroxyethyl acrylate (M-5400), 5 parts ofdipentaerythritol hexaacrylate (M-400), 25 parts of toluene, and 3 partsof a photo-initiator (IRGACURE 184). The curable composition was appliedonto a plasma-treated PET plate (a thickness of 100 μm) by spraying.After evaporation of the solvent, the curable composition was cured byirradiation with a light of integral light intensity of 300 mJ/cm² toform a layer (a thickness of 100 μm) comprising the curable composition.Subsequently, a coating agent (Applying liquid B) containing 10 parts ofdipentaerythritol hexaacrylate (M-400), 100 parts of a titaniumdioxide-dispersed liquid (15% toluene solution), 100 parts of toluene,and 0.3 parts of a photo-initiator (IRGACURE 184) was applied on thecured layer by spin coating. The coating agent was cured by irradiationwith a light of integral light intensity of 600 mJ/cm² to form a layer(a thickness of 0.1 μm) having a medium refractive index. Furthermore, acoating agent (Applying liquid C) containing 10 parts ofdipentaerythritol hexaacrylate (M-400), 200 parts of a titaniumdioxide-dispersed liquid (15% toluene solution), and 0.3 parts of aphoto-initiator (IRGACURE 184) was applied on the layer having a mediumrefractive index by spin coating, and the coating agent was cured byirradiation with a light of integral light intensity of 600 mJ/cm² toform a layer (a thickness of 0.1 μm) having a high refractive index.Finally, a coating agent (Applying liquid A) containing 100 parts ofOPSTAR JM5010 and 0.3 parts of a photo-initiator (IRGACURE 184) wasapplied on the layer having a high refractive index by spin coating. Thecoating agent was cured by irradiation with a light of integral lightintensity of 400 mJ/cm² to form a layer (a thickness of 0.1 μm) having alow refractive index, whereby the desired antireflection film wasobtained.

Example 38

A coating agent (Applying liquid D) obtainable by dissolvingperfluorotrimethoxysilane in a fluorinated solvent (“FLUORINERT FC-77”,a trade name of 3M Co., Ltd.) was applied by spin coating on the layerhaving a low refractive index of the antireflection film obtained inExample 34 and was dried and cured to form an over-coating layer (athickness of 0.1 μm), whereby the desired antireflection film wasobtained.

Comparative Example 13

A coating agent obtainable by mixing 80 parts of dipentaerythritolhexaacrylate (M-400), 20 parts of tetrahydrofurfuryl acrylate, 100 partsof toluene, and 3 parts of a photo-initiator was applied onto aplasma-treated PET plate (a thickness of 100 μm) by means of a barcoater. After evaporation of the solvent, the coating agent was cured byirradiation with a light of integral light intensity of 600 mJ/cm² toform a hard-coating layer (a thickness of 5 μm). Subsequently, a coatingagent (Applying liquid A) containing 100 parts of OPSTAR JM5010 and 0.3parts of a photo-initiator (IRGACURE 184) was applied on thehard-coating layer by spin coating. The coating agent was cured byirradiation with a light of integral light intensity of 400 mJ/cm² toform a layer (a thickness of 0.1 μm) having a low refractive index,whereby the desired antireflection film was obtained.

Comparative Example 14

A coating agent obtainable by mixing 80 parts of dipentaerythritolhexaacrylate (M-400), 20 parts of tetrahydrofurfuryl acrylate, 100 partsof toluene, and 3 parts of a photo-initiator was applied onto aplasma-treated PET plate (a thickness of 100 μm) by means of a barcoater. After evaporation of the solvent, the coating agent was cured byirradiation with a light of integral light intensity of 600 mJ/cm² toform a hard-coating layer (a thickness of 5 μm). Subsequently, a coatingagent (Applying liquid B) containing 10 parts of dipentaerythritolhexaacrylate (M-400), 100 parts of a titanium dioxide-dispersed liquid(15% toluene solution), 100 parts of toluene, and 0.3 parts of aphoto-initiator (IRGACURE 184) was applied on the hard-coating layer byspin coating. The coating agent was cured by irradiation with a light ofintegral light intensity of 600 mJ/cm² to form a layer (a thickness of0.1 μm) having a medium refractive index. Furthermore, a coating agent(Applying liquid C) containing 10 parts of dipentaerythritolhexaacrylate (M-400), 200 parts of a titanium dioxide-dispersed liquid(15% toluene solution), and 0.3 parts of a photo-initiator (IRGACURE184) was applied on the layer having a medium refractive index by spincoating, and the coating agent was cured by irradiation with a light ofintegral light intensity of 600 mJ/cm² to form a layer (a thickness of0.1 μm) having a high refractive index. Finally, a coating agent(Applying liquid A) containing 100 parts of OPSTAR JM5010 and 0.3 partsof a photo-initiator (IRGACURE 184) was applied on the layer having ahigh refractive index by spin coating. The coating agent was cured byirradiation with a light of integral light intensity of 400 mJ/cm² toform a layer (a thickness of 0.1 μm) having a low refractive index,whereby the desired antireflection film was obtained.

Comparative Example 15

A coating agent comprising 100 parts of polycaprolactone tetraol(“PLACCEL 410D”, a trade name of Daicel Chemical Industries, Ltd.), 75parts of hexamethylene diisocyanate (D-170N), and 75 parts of toluenewas applied onto a plasma-treated PET plate (a thickness of 100 μm) byspraying, and was dried at 140° C. for 30 minutes to form a softpolyurethane layer (a thickness of 100 μm). Subsequently, a coatingagent (Applying liquid A) containing 100 parts of OPSTAR JM5010 and 0.3parts of a photo-initiator (IRGACURE 184) was applied on the softpolyurethane layer by spin coating. The coating agent was cured byirradiation with a light of integral light intensity of 400 mJ/cm² toform a layer (a thickness of 0.1 μm) having a low refractive index,whereby the desired antireflection film was obtained.

On each of the antireflection films of Examples 36 to 38 and ComparativeExamples 13 to 15, average reflectance was measured and also impactresistance, flexure resistance, and productivity were evaluated. Theresults are shown in Table 8. Average reflectance is a value in therange of 450 to 650 nm on a spectrophotometer. Impact resistance wasevaluated by examining under conditions of 1/4 φ and 500 g×50 cm using aDu Pont-type impact-testing machine. Flexure resistance was evaluated byfolding a test plate (an antireflection film) to 0T. Productivity wasrepresented by a symbol ◯ in the case where the film was producible(curing and drying) by the second and a symbol X in the case where thefilm was producible by the minute. Each of Applying liquids A to D wasapplied onto a silicon wafer by spin coating and the refractive indexwas measured by an ellipsometer. The refractive indexes of Applyingliquids A, B, C, and D were found to be 1.36, 1.71, 1.90, and 1.35,respectively.

TABLE 8 Comparative Comparative Comparative Example 36 Example 37Example 38 Example 13 Example 14 Example 15 Average reflectance 1.71%1.08% 0.62% 1.74% 1.04% 1.69% Impact resistance ∘ ∘ ∘ x x ∘ Flexureresistance ∘ ∘ ∘ x x ∘ Productivity ∘ ∘ ∘ ∘ ∘ x

INDUSTRIAL APPLICABILITY

The active energy ray-curable urethane (meth)acrylate and activeenergy-ray curable composition of the present invention can be used ascoating agents and paints having abrasion resistance and lubricity.

What is claimed is:
 1. An active energy ray-curable urethane(meth)acrylate which has an alkyl group having 13 to 25 carbon atoms andan active energy ray-curable functional group and is modified withpolycaprolactone.
 2. The active energy ray-curable urethane(meth)acrylate according to claim 1, which is obtained by reacting anorganic isocyanate having three or more isocyanate groups in onemolecule, an alkyl alcohol having 13 to 25 carbon atoms, and apolycaprolactone-modified hydroxyethyl (meth)acrylate.
 3. The activeenergy ray-curable urethane (meth)acrylate according to claim 2, whereinthe molar ratio of the isocyanate group of the organic isocyanate, thehydroxyl group of the polycaprolactone-modified hydroxyethyl(meth)acrylate, and the hydroxyl group of the alkyl alcohol is 1:0.8 to1.20:0.02 to 0.33.
 4. An active energy-ray curable compositioncomprising: an active energy ray-curable urethane (meth)acrylate whichhas an alkyl group having 13 to 25 carbon atoms and an active energyray-curable functional group and is modified with polycaprolactone; andat least one compound selected from the group consisting of organicbeads, inorganic beads, an antistatic agent, and a compound having anactive energy ray-curable functional group copolymerizable with theurethane (meth)acrylate.
 5. A functional material obtained by curing anactive energy ray-curable urethane (meth)acrylate which has an alkylgroup having 13 to 25 carbon atoms and an active energy ray-curablefunctional group and which is modified with polycaprolactone, whereinsaid curing is by irradiation with an active energy ray.
 6. A functionalmaterial obtained by curing active energy-ray curable composition byirradiation with an active energy ray, the composition comprising: anactive energy ray-curable urethane (meth)acrylate which has an alkylgroup having 13 to 25 carbon atoms and an active energy ray-curablefunctional group and is modified with polycaprolactone; and at least onecompound selected from the group consisting of organic beads, inorganicbeads, an antistatic agent, and a compound having an active energyray-curable functional group copolymerizable with the urethane(meth)acrylate.
 7. A light-diffusive sheet comprising: a substratesheet; and a cured layer made of an active energy ray-curable urethane(meth)acrylate, which is formed on a surface of the substrate sheet. 8.A light-diffusive sheet comprising: a substrate sheet; and a cured layermade of an active energy ray-curable composition, which is formed on asurface of the substrate sheet.
 9. An antireflection film comprising: asubstrate film; a cured layer made of an active energy ray-curableurethane (meth)acrylate, which is formed on a surface of the substratefilm; and an antireflection layer provided on the cured layer.
 10. Anantireflection film comprising: a substrate film; a cured layer made ofan active energy ray-curable composition, which is formed on a surfaceof the substrate film; and an antireflection layer provided on the curedlayer.
 11. An active energy ray-curable urethane (meth)acrylate whichhas an alkyl group having 13 to 25 carbon atoms and terminal methylenegroup and wherein said active energy ray-curable urethane (meth)acrylateis modified with polycaprolactone.
 12. A process for producing an activeenergy ray-curable urethane (meth)acrylate comprising steps of: mixingan organic isocyanate having three or more isocyanate groups in onemolecule, an alkyl alcohol having 13 to 25 carbon atoms; heating themixture; adding a polycaprolactone-modified hydroxyethyl (meth)acrylateto the mixture; and maintaining the mixture at 70° C. for 3 hours.